Yarn conditioning process



Patented Apr. 23, 1940 UNITE STATES PATENT YARN CONDITIONING PROCESS Jersey No Drawing. Application December 21, ,1938,

Serial No. 247,094

7 Claims.

This invention relates to the conditioning of textile yarns and more particularly to the conditioning of filaments and yarns composed of organic derivatives of cellulose such as cellulose acetate, cellulose proplonate, cellulose acetate propionate, and cellulose acetate butyrate, to render them more amenable to textile operations such as knitting and the like.

As is well known in the manufacture of yarns,

particularly those composed of or containing cellulose organic derivatives, it is necessary to treat the yarn in order to reduce the tendency toward breakage of the individual filaments or fibers when they are subjected to various melo chanical strains and to lubricate the yarn in order to facilitate handling in such operations as spinning, twisting, Winding and reeling. It is also necessary to treat yarn to adapt it for use as warp or filling or for the manufacture of various types of knitted fabrics. In knitting, it is particularly important that the yarn ,be soft and pliable in order that it may conform readily to the contour of the needles and thus produce a closely knit fabric free from such defects as stitch distortion", pin holes, laddering, and the like.

Heretofore it has been proposed to employ softening agents such as polyhydric alcohols and similar agents as ingredients of yarn conditioning or lubricating formulas, generally in connection with mineral, animal or vegetable oils.

It has been found, however, that most of the known softening agents and the various formulas containing them have certain drawbacks, one of the most serious of which is high vapor pressure, and in some cases'too drastic a solvent action on the yarn. Many of such agents possess slight or insufficient solvent power for the, lubricants with'which they are used, and it is accordingly necessary to employ blending agents or emulsifying agents in order to obtain operable yarn treating formulas. In addition, many of the known softening and lubricating agents are insufficiently soluble in water to permit sat isfactory removal by aqueous scour baths.

This invention has as its principal object to provide an entirely new class of yarn conditioning agents which are particularly adapted for the treatment of yarns composed of or containing organic derivatives of cellulose and capable of lubricating, softening and rendering such yarns more amenable'to knitting and other textile operations. A further. and specific object is to provide a class. of conditioning agents which or augment or assist the lubricating action of various lubricants when applied to such yarns. A. still further object is to provide yarn softening and lubricating formulas'which'can be readily removed from the yarns by the usual scour baths. A still further object is to provide an improved method for the conditioning of yarns, particularly those composed of or containing organic derivatives of cellulose such as cellulose acetate, whereby the yarn is rendered soft and pliable and capable of employment in a variety of textile operations where complicated designs or stitches are employed. Another object is to provide an improved. type of yarn which is especially amenable to textile operations including circular knitting, weaving, spinning and the like. Other objects will appear hereinafter.

These objects are accomplished by the following invention which, in its broader aspects, comprises the discovery that esters of furoic and tetrahydrofuroic acid having the formula:

wherein R is a furan or tetrahydrofuran group and where R is a substituent selected from the group consisting of substituted and unsubstituted alkyl, cycloalkyl, heterocyclic and aryl groups; and wherein n is a small whole number, may be used as yarn conditioning agents and particularly as softening agents, with or without the addition of animal, mineral, or vegetable oils, in the treatment of yarns composed of orcontaining organic derivatives of cellulose. We have found that these compounds when employed as described in the detailed examples set forth below have a slight solvent and/or softening action on cellulose organic derivative yarns which renders such yarns soft and pliable without at the same time having too drastic an action thereon.

Typical examples of compounds which, in accordance with our invention, we have found to be valuable yarn-treating agents are given in the following table. These compounds may be prepared as follows: (1) By action of furoyl or tetrahydrofuroyl chloride on a suitable alcohol with or without basic material. (2) By esterification of the two acids-using the desired carbinol'anda catalyst such as sulfosalicylic acid, p-toluene sulfonic acid, sulfuric acid, etc. (3)

By esterification as in (2) using a third component such as toluene, xylene, ethylene chloride,

(4) 'By action of alkylene oxides such as Trimethylene glycol ditetrahydroiuroate hydroxy-alkyl, etc., derivatives. (5) By hydrogenation of esters of furoic acid to obtain esters of tetrahydrofuroic acid using nickel, copper chromite, etc.

Esters of furo'ic and tetrahydrofuroic acids FUROA'IES Monofi-hydroxyethyl furoate'. Ethoxyethoxyethyl furoate. Butoxyethyl furoate B toxyethoxyethyl furoatc. T trahydorfurfuryl iuroate Trimethylene glycol difuroate.... Glyceryl difuroete, mp 978.

TETRAHYDROFUR OATES Butoxyethyl tetrahydrofuroate Tetrahydrofurfuryl tetrahydrofuroete. Ethoxyethoxyethyl tetrahydrofuroate... Ethylene glycol ditctrahydroluroate b Diethylene glycol ditetrahydroiuroate.

'lriethylene glycol d1tetrahydrofuroate Butoxyeth oxyethyl tetrahydrofuroate. Glyceryl ditetrahydrofuroate Glyceryl acetate ditetrahydrofuroate Examples of the preparation of typical compounds of this type are as follows:

Preparation of diethylene glycol di-furoate Preparation of p-hydroxyethyl furoate Five moles furoyl chloride are added dropwise to 6 moles sodium bicarbonate in ten moles eth-, ylene glycol, with vigorous stirring at room temperature. The mixture is stirred forthree hours, filtered and distilled. The ester boils at 160- /10 mm.

Or, five moles of furoic acid are placed in a bomb with a slight excess of ethylene oxide. The bomb is then heated at 100 until the pressure has dropped 20-30 lbs/sq. in. The product is then worked up in the usual way. Nickel, zinc,

or dialkyl sulfates may be used as catalysts.

Preparation of tetrahydrofurfuryl furoate Nine moles of furoic acid, 10 moles tetrahydrofurfuryl alcohol, 5 g. p-toluene sulfonic acid and 1 liter toluene are placed in a flask. The toluene and water are distilled ofi and separated, the toluene being returned to the reaction. The distillation is continued until the theoretical quantity of water has been collected. The residue in the flask is then washed with bicarbonate solution and distilled. The ester is obtained in a 70-5% yield, and its boiling point is'153-8/ 10 mm. It is insoluble in water.

Preparation of tetrahydrojurjuryl tetrahydrofuroate Three moles of the above ester and 15 g. Raney nickel are placed in a bomb and shaken with hydrogen under 1600 lbs. pressure at 150-60 for five hours. The reaction is then complete and the product is filtered from the catalyst and distilledin vacuum. The ester "has a boiling point at 152-5/12 mm. It is about 8-10% soluble in water.

Preparation of triethylene glycol di-furoate Two kg. of furoyl chloride and a solution of 620 g. sodium hydroxide in 2.5 liters water are added simultaneously to 1 kg. triethylene glycol at 205, over a period of 5 hours. The mixture is then stirred for 8 hours at this temperature and made alkaline with more hydroxide. The ester boils at 255-'l0/ 13 mm. and melts at 61-3".

Preparation of ethylene glycol di-tetrah'ydrojuroate Five moles of ethylene glycol, ten moles tetrahydrofuroic acid, 5 g. of p-toluene sulfonic acid, and one liter of xylene are distilled. The xylene is separated from the water and returned continuously to the reaction. Afterten moles of water are collected, the mixture is washed with bicarbonate solution and distilled. The ester boils at 210-5/13 mm.

In accordance with the invention these compounds may be applied directlyto the yarn during or after spinning, or may be added to the spinning solution itself. We have found that these compounds have exceptional solvent powers which enable them to dissolve mineral oils and blown and unblown, drying and semi-drying, vegetable and animal oils and accordingly they may be, and preferably are, employed as ingredients of yarn conditioning or lubricating formulas in conjunction with agents which function wholly or partially as lubricants.

In the following examples and description we have set forth several of the preferred embodiments of our invention, but they are included merely for purposes of illustration and not as a limitation thereof.

Our invention will be more readily understood by reference to the following examples in which typical applications of the invention are set forth.

Example 1.A 20% solution of cellulose acetate in acetone in which is incorporated 1-25% by weight of the cellulose acetate of carbitol tetrahydrofuroate is extruded through fine orifices into an evaporative atmosphere. The filaments thus produced are wound or twisted and wound. -Yarns produced from filaments thus prepared are pliable and suitable for knitting.

Example 2.Tetrahydrofurfuryl tetrahydrofuroate is applied 'to textile materials (silk, cotton, wool, cellulose acetate, viscose, etc.) by means of a bath, wick, roller, spray, etc., to'facilitate their knitting, weaving, spinning and the like. If the yarn is intended primarily for knitting, the amount of conditioning liquid applied may vary from 4-25% by weight. If the yarn is intended for weaving, the amount of conditioning liquid may vary between by weight of the yarn. I

Example 3.-A conditioning liquid is made up as follows:

Parts Carbltolfuroa e '70 Olive oil -30 and applied to textile materials such as silk, wool, cellulose acetate, viscose, etc., as described in Example 2. If the yarn is intended primarily for knitting, the amount of the conditioning liquid may vary from 4-25% by weight of the yarn:

and if the yarn isintended for weaving, the amount of liquid may vary between 1-5% by weight of the yarn. Cellulose acetate yarn treated as described above is quite soft and pliable and gives improved results in various textile operations such as weaving, knitting, etc.

Other examples of yarn conditioning compositions which may be applied to various types of yarns, particularly those composed of or containing cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, and similar cellulose organic acidesters in accordance with our invention and which render such yarns soft and pliable and especially well adapted for various textile operations, particularly knitting, are as follows:

Example 4:

Diethylene glycolditetrahydrofuroate Blown olive oil 40 Example 5: Triethylene glycolditetrahydrofuroate- 70 Neats-foot oil 30 Example 6:

Triethylene glycolmonotetrahydrofuroate '70 Sperm oil 30 Example 7:

Diethylene glycolacetate tetrahydrofuroate '70 Blown neats-foot oil 30 Example 8:

Triethylene glycolmonofuroate 50 Blown sperm oil 50 Example 9:

Water soluble cellulose ester 10 Water 80 Triethylene glycoltetrahydrofuroate acetate 10 Example 10:

Tetrahydrofurfuryl furoate 80 Mineral oil 20 Example 11:

Tetraethylene glycol furoate 20 Gelatin 10 Water Sulfonated castor oil 5 Any of the above compositions may be applied to the yarn by means of a bath, wick, spray, roller, pad or any suitable means. The amount of conditioning liquid applied may vary between 5-25% by weight of the yarn. Usually, however, the amount of conditioning liquid applied is about 10-l5% by weight of the yarn. Yarn composed of cellulose acetate conditioned as described above gives excellent results when used in the circular knitting process.

As will be apparent from the above examples and description the conditioning agents of our invention may be applied by a wide variety of methods. For example, we may employ the agent as an ingredient of the spinning dope from which the filaments are formed, the amount of the agent so employed depending upon a number of factors, such as the particular cellulose derivative used in making the yarn, the solvent or solvent combination used in making up the spinning solution, and the degree of softness or pliability desired in the yarn, etc.

If the conditioning agent is to be applied to the yarn after spinning, this may be done by bringing the yarn in contact with a wick, roll, 01' felt wet therewith, or the liquid may be applied by immersion, spray, or otherwise. The particular point at which the liquid isapplied the case of staple fiber manufacture, the liquid may be applied to the yarn prior to, or after cutting into staple lengths.

The amount of the agent so employed will vary widely depending upon the results desired, the specific nature of the material to which the agent is applied, the use to which the yarn is eventually to be put and other factors. For example, in a given case where a cellulose organic acid ester yarn such as a yarn composed of cellulose acetate, is intended for knitting, about 4 to 25% or more by weight, based on the weight of the dry yarn, may be satisfactory, while if the yarn is intended for weaving, the amount may vary between about land 5%.

Although in the above examples .we have referred primarily to yarn treating compositions containing only the conditioning agent and an oil, other ingredients such as solvents, non-solvents, emulsifying agents, blending agents and the like, may be added within the scope of our invention. Likewise, various dyes or other coloring matter may be included in case it is desired-to permanently or fugitively tint ordye the material undergoing treatment.

Although we have found it convenient to illustrate our invention by reference to compositions containing specific percentages of the various in formulas described herein are applicable to the conditioning of many other types of cellulose derivative yarns such as those composed of or containing cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate, ethyl cellulose, methyl cellulose, benzyl cellulose and others, as well as to the conditioning of silk, Wool, cotton, viscose and other natural or artificial materials,

The term yarn as used herein and in the claims is to be understood as including a single filament, a purality of filaments associated into the form of a thread, either of high or low twist, single or multiple threads associated or twisted together, composite threads composed of a mixture of natural and artificial filaments or a compositethread formed by twisting together individual strands of natural or artificial materials, as well as cut staple fibers produced from natu ral and/or artificial filaments or threads and spun yarn produced from such staple fibers.

As indicated above, the yarn conditioning agents of our invention are exceptionally good solvents for a wide variety of mineral, blown and unblown, drying and semi-drying animal and vegetable oils such as cottonseed, olive, castor,

neats-foot, sperm and other oils. This enables them to be used with any of such oils in making up a variety of yarn treating formulas of varying composition.

The yarn conditioning method and compositions of our invention possess many outstanding advantages. The fundamental and outstanding characteristic of the agents employed in accordance with the invention is their ability to soften yarns, especially those composed of or containing organic derivatives of cellulose such as cellulose acetate and render them soft and pliable and amenable to various textile operations, especially operations such as those involved in weaving and knitting where complicated designs or stitches are employed, without too drastic an action on the yarn material. Another outstanding characteristic of these compounds is their exceptional solvent power for a wide variety of mineral, animal, and vegetable oils and their ability to act as lubricating assistants in conjunction with these oils when applied to such yarns. In addition, due to their solubility in water, they may be readily removed from yarns and fabrics by means ofthe usual aqueous scour baths. By employing the yarn conditioning agents and method of our invention as herein described, one is enabled to obtain highly satisfactory results in the manufacture of yarns and woven fabrics and especially the production from these yarns of closely knit fabrics free from defects such as pin holes, stitch distortion, laddering and the like.

What we claim and desire to secure by Letters Patent of the United States is:

1. The process of conditioning yarn to render it more amenable to textile operations incjuding knitting, weaving, spinning and the like, which comprises applying thereto a lubricating and softening composition containing as its essential lubricating and softening component an ester derived from an acid of the group consisting of furoic and tetrahydrofuroic acids, selected from the group consisting of mono-B-hydroxyethyl furoate, ethoxyethoxyethyl furoate, butoxyethyl furoate,,butoxyethoxyethyl furoate, glycol furoate, diethylene glycol difuroate, triethylene glycol difuroate, trimethylene glycol difuroate, glyceryl difuroate, butoxyethyl tetrahydrofuroate, ethoxyethoxyethyl tetrahydroiuroate, ethylene glycol ditetrahydrofuroate, diethylene glycol ditetrahydrofuroate, trimethylene glycol ditetrahydrofuroate, triethylene glycol ditetrahydrofuroate, butoxyethoxyethyl tetrahydrofuroate, glyceryl ditetrahydrofuroate, and glyceryl acetate ditetrahydrofuroate.

2. The process of conditioning yarn composed of organic derivatives of cellulose to render it more amenable to textile operations including knitting, weaving, spinning and the like, which comprises applying thereto a lubricating and softening composition containing as its essential lubricating and softening component an ester derived from an acid of the group consisting of furoic and tetrahydrofuroic acids selected from the group consisting of mono-B-hydroxyethyl furoate, ethoxyethoxyethyl furoate, butoxyethyl furoate, butoxyethoxyethyl furoate, glycol furoate, diethylene glycol difuroate, triethylene glycol difuroate, trimethylene glycol difuroate, glyceryl difuroate, butoxyethyl tetrahydrofuroate, ethoxyethoxyethyl tetrahydrofuroate, ethylene glycol ditetrahydrofuroate, diethylene glycol ditetrahydrofuroate, trimethylene .glycol ditetrahydrofuroate, triethylene glycol ditetrahydrofuroate, butoxyethoxyethyl tetrahydrofuroate, glyceryl ditetrahydrofuroate, and glyceryl acetate ditetrahydrofuroate.

3. The process of conditioning yarn composed furoate, glycol furoate, diethylene glycol difuroate, triethylene glycol difuroate, trimethylene 'glycol difuroate, glyceryl difuroate, butoxyethyl tetrahydrofuroa'te, ethoxyethoxyethyl tetrahydro furoate, ethylene glycol ditetrahydrofuroate, di-

; ethylene glycol ditetrahydrofuroate, trimethylene glycol ditetrahydrofuroate, triethylene glycol ditetrahydrofur'oate, butoxyethoxyethyl tetrahydrofuroate glyceryl ditetrahydrofuroate, and glyceryl acetate ditetrahydrofuroate' 4, The process of conditioning yarn composed of cellulose acetate to render it more amenable to textile operations including knitting, weaving, spinning, and the like, which comprises applying thereto a lubricating and softening composition containing as its essential lubricating and softening component an ester derived from an acid of the group consisting of furoic and tetrahydrofuroic acids selected from the group consisting of mono-p-hydroxyethyl furoate, ethoxyethoxyethyl furoate, butoxyethyl furoate, butoxyethoxyethyl furoate, glycol. furoate, diethylene glycol difuroate, triethylene glycol difuroate, trimethylene glycol difuroate, glyceryl difuroate, butoxyethyl tetrahydrofuroate, ethoxyethoxyethyl tetrahydrofuroate, ethylene glycol ditetrahydrofuroate, diethylene glycol ditetrahydrofuroate, trimethylene glycol ditetrahydrofuroate, triethylene glycol ditetrahydrofuroatep butoxyethoxyethyl tetrahydrofuroate, glyceryl ditetrahydrofuroate, and glyceryl acetate ditetrahydrofuroate, and a textile lubricant.

5. Textile yarns amenable to textile operations including knitting, weaving, spinning and the like, impregnated with a lubricant containing as its essential lubricating and softening component an ester derived from an acid of the group consisting of furoic and tetrahydrofuroic acids selected from the group consisting of mono-(ihydroxyethyl furoate, ethoxyethoxyethyl furoate, butoxyethyl furoate, butoxyethoxyethyl furoate, glycol furoate, diethylene glycol difuroate, triethylene glycol difuroate, trimethylene glycol difuroate, glyceryl difuroate, butoxyethyl tetrahydrofuroate, ethoxyethoxyethyl tetrahydrofuroate, ethylene glycol ditetrahydrofuroate, diethylene glycol ditetrahydrofuroate, trimethylene glycol ditetrahydrofuroate, triethylene glycol ditetrahydrofuroate, butoxyethoxyethyl tetrahydrofuroate, glyceryl ditetrahydrofuroate, and glyceryl acetate ditetrahydrofuroate.

6. Textile yarns composed of organic derivatives of cellulose amenable to textile operations including knitting, weaving, spinning, and the like impregnated with a conditioning agent comprising an ester derived from an acid of the group consisting of furoic and tetrahydrofuroic acids selected from the group consisting of mono-phydroxyethyl furoate, ethoxyethoxyethyl furoate, butoxyethyl furoate, butoxyethoxyethyl furoate, glycol furoate, diethylene glycol difuroate, triethylene glycol difuroate, trimethylene glycol difuroate, glyceryl difuroate, butoxyethyl tetrahydrofuroate, ethoxyethoxyethyl tetrahydrofuroate, ethylene glycol ditetrahydrofuroate, diethylene glycol ditetrahydrofuroate, trimethylene glycol ditetrahydrofuroate, triethylene glycol ditetrahydrofuroate, butoxyethoxyethyl tetrahydrofuroate, glyceryl ditetrahydrofuroate', and glyceryl acetate ditetrahydrofuroate.

7. Textile yarns composed of organic derivatives of cellulose amenable to textile operations including knitting, weaving, spinning, and the like impregnated with aconditioning agent comprising an ester derived from an acid of the group consisting of furoic and tetrahydrofuroic acids selected from the group consisting of mono-#- hydroxyethyl furoate, ethoxyethoxyethyl furoate,

butoxyethyl furoate, butoxyethoxyethyl fu1'oate,.

glycol furoate, diethylene glycol difuroate, tri-' ethylene glycol difuroat'e, trimethylene glycol difuroate, glyceryl difuroate, butoxyethyl tetrahydrofuroate, ethoxyethoxyethyl tetrahydrofuroate, ethylene glycol ditetrahydrofuroate, diethylene glycol ditetrahydrofuroate, trimethylene glycol ditetrahydrofuroate, triethylene glycol ditetrahydrofuroate, butoxyethoxyethyl tetrahydrofuroate, glyceryl ditetrahydrofuroate; and glyceryl acetate ditetrahydrofuroate, and a textile lubricant.

JOSEPH B. DICKEY.

JAMES G. McNALLY. 

